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Article history: We investigated arsenic removal from groundwater by electrocoagulation (EC) using aluminum as the
Received 19 November 2012 sacrificial anode in a pre-pilot-scale continuous filter press reactor. The groundwater was collected at a
Received in revised form depth of 320 m in the Bajío region in central Mexico (arsenic 50 μg L–1, carbonates 40 mg L–1, hardness
6 April 2013
80 mg L–1, pH 7.5 and conductivity 150 μS cm–1). The influence of current density, mean linear flow and
Accepted 15 April 2013
Available online 24 April 2013
hypochlorite addition on the As removal efficiency was analyzed. Poor removal of total arsenic (o 60 %)
in the absence of hypochlorite is due to a mixture of arsenite (HAsO2(aq) and H3AsO3(aq)) and arsenate
Keywords: (HAsO42−). Arsenic removal is more efficient when arsenite is oxidized to arsenate by addition of
Arsenic removal hypochlorite at a concentration typically used for disinfection (1 mg L–1). Arsenate removal by EC might
Aluminum sacrificial anode
involve adsorption on aluminum hydroxides generated in the process. Complete arsenate removal by
Dissolution
EC was satisfactory at a current density of 5 mA cm–2 and mean linear flow of 0.91 cm s–1, with
Electrolysis
Coagulation electrolytic energy consumption of 3.9 kWh m3.
Precipitation & 2013 Elsevier Ltd. All rights reserved.
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.04.029
2 O.J. Flores et al. / Chemical Engineering Science 97 (2013) 1–6
effective in destabilizing dispersed fine particles and anions Al(OH)3 and Al2O3 flocs are believed to adsorb HAsO2− 4 (Hernández
contained in water (Chen et al., 2002). Flocs of metallic hydroxides et al., 2010; Kobya et al., 2011; Mohora et al., 2012)
are formed and remove dissolved species (Chen et al., 2002; Shen
Al(OH)3(s)+HAsO2– 2–
4 -[Al(OH)3 HAsO4 ](s) (4)
et al., 2003; Hernández et al., 2010; Mohora et al., 2012).
Arsenic species in water from deep wells (pH∼7.5) include Al2O3(s)+HAsO2– 2–
4 -[Al2O3 HAsO4 ](s) (5)
innocuous arsenite (HAsO2 and H3AsO3, oxidation state III) and
arsenate anions (HAsO42–, oxidation state V) (Pourbaix, 1974; We previously reported that arsenite removal may occur by
Smedley and Kinniburgh, 2002). Arsenate at neutral pH is more sweep coagulation, in which interaction occurs between As(III)
susceptible to EC removal (Hansen et al., 2007; Hernández et al., and Al(OH)3 and Al2O3 flocs (Hernández et al., 2010). However,
2010; Wan et al., 2011; Mohora et al., 2012; Balasubramanian et al., reports on the mechanism of As removal by aluminum flocs are
2009) because arsenate anions adsorb onto flocs of iron (Hansen rather limited. A deeper understanding of the As interaction with
et al., 2007, 2008; Kobya et al., 2011; Wan et al., 2011) and aluminum precipitates requires additional research.
aluminum hydroxides (Hansen et al., 2008; Hernández et al., At the aluminum cathode, hydrogen gas is released
2010; Kobya et al., 2011; Mohora et al., 2012). Martínez-Villafañe
3H2O+3e–-1.5H2+3OH– (6)
et al. (2009) and Kobya et al. (2011) reported that arsenate removal
occurs via ligand exchange with ferric hydroxides. According to The solution at the cathode interface becomes alkaline over
van Genuchten et al. (2011), As(V) forms inner-sphere complexes time. OH– ions migrate and diffuse away from the cathode to the
with the surface of iron oxides. However, reports on the mechan- anode, thus favoring water formation by reaction with protons
ism of As removal by aluminum flocs are rather limited. Hansen from reaction (2) to (3)
et al. (2007) reported that oxidation of As(III) to As(V) by ferric
ions and/or oxygen bubbling is convenient. OH–+H+-H2O (7)
The electrode materials commonly used for As removal by EC The major problem with aluminum anodes is passivation due
are mainly iron (Parga et al., 2005; Hansen et al., 2007, 2008; to Al2O3 precipitation, which leads to high anode and cell
García-Lara and Montero-Ocampo, 2010; Kobya et al., 2011; Wan potentials and increases the energy consumption and cost of EC
et al., 2011) and aluminum (Hernández et al., 2010; Kobya et al., (Kobya et al., 2011; Mohora et al., 2012). Passivation can be
2011; Mohora et al., 2012). Kobya et al. (2011) demonstrated that controlled at low current densities in combination with convection
aluminum was better than iron electrodes at removing arsenic (turbulent flow conditions), which favors Al3+ transport away from
from drinking water. We obtained similar results in a previous the surface to the bulk solution. In addition, cathodes of the same
study (Hernández et al., 2010). material can be used to electrodissolve Al2O3 by periodic current
There are literature reports on EC removal of As using Al reversal (Mohora et al., 2012), which allows even consumption of
electrodes from synthetically prepared water (Hernández et al., the aluminum electrodes during the process.
2010; Kobya et al., 2011) and groundwater (Mohora et al., 2012)
containing high arsenic concentrations. The results differ because
a great number of species that are present in groundwater 3. Experimental
interfere with arsenic removal, besides reactor operating para-
meters such as current density, flow rate and geometry. 3.1. Solutions
The aim of this study was to decrease the arsenic concentration
in groundwater from the Bajío region by EC using aluminum as the Groundwater for electrochemical treatment was collected from
sacrificial anode in a pre-pilot-scale continuous filter press reactor. deep wells (320 m) located in the Bajío region (Guanajuato, México).
The influence of current density, mean linear flow rate and Table 1 lists the characteristics of the sample. The groundwater
hypochlorite addition on the As removal efficiency was analyzed. contained 50 μg L–1 total As, which exceeds the Mexican standard for
The energy consumption for electrolysis was also estimated. arsenic in water (25 μg L–1). It is believed that As(III) is predominant
in this anaerobic groundwater. Water samples were obtained from
the wells before the disinfection process, which usually involves
2. Electrochemical and chemical processes during As removal
hypochlorite addition.
by EC using aluminum electrodes
EC involves in situ generation of coagulants by electrodissolu- 3.2. Pre-pilot-scale filter press cell
tion of aluminum electrodes. Aluminum cations are generated at
the anode and hydrogen gas is evolved at the cathode. This process Fig. 1 shows a schematic of the experimental set-up.
generates aluminum hydroxide, which is believed to adsorb As The system consists of a continuous pre-pilot-scale filter press
(Hernández et al., 2010; Kobya et al., 2011; Mohora et al., 2012). cell in which the coagulant is produced. The resulting solution
The electrode and chemical reactions in neutral solution (pH∼7)
are shown below. At the anode, electrodissolution generates
aluminum ions (Al3+), which are transformed to aluminum hydro-
xide and aluminum oxide in the bulk Table 1
Characteristics of the groundwater samples collected at a depth of 320 m in the
Al(s)-Al3++3e– (1) Bajío region (Guanajuato, México).
3.3. Methodology
Fig. 2. Influence of the mean linear flow rate on the residual arsenic concentration
and aluminum dose for fresh groundwater (initial parameters: arsenic 50 μg L–1,
carbonates 40 mg L–1, hardness 80 mg L–1, pH 7.5 and conductivity 150 μS cm–1) at a
current density of (a) 4, (b) 5 and (c) 6 mA cm–2. The anode area for six channels
was 148.2 cm2.
H2O-0.5O2+2H++2e– (9)
At 4 mA cm–2, CAs increased linearly between 3 and 38 μg L–1 as corresponding to an aluminum dose of 9–17 mg L–1 and an
a function of u in the interval 0.91–4.55 cm –1 due to a decrease in aluminum dose rate of QAl(III) ¼0.32–0.34 mg L–1 s–1, evaluated as
the experimental aluminum dose from 17 to 1 mg L–1 (Fig. 3a).
C AlðIIIÞ u
However, the CAs values are lower than those obtained for fresh Q AlðIIIÞ ¼ ð11Þ
LN
groundwater at 4 mA cm–2 (Fig. 2a). This confirms the hypothesis
that HAsO42− is probably removed by adsorption on Al(OH)3 and EC at 5 mA cm–2 satisfied the Mexican As standard at flow rates
Al2O3 flocs (Hernández et al., 2010; Kobya et al., 2011; Mohora between 0.91 and 2.73 cm s–1, corresponding to aluminum doses
et al., 2012). X-Ray absorption spectroscopy and X-ray photoelec- of 6–31 mg L–1and aluminum dose rates of 0.34–0.58 mg L–1 s–1.
tron spectroscopy would be helpful in investigating the local EC at 6 mA cm–2 satisfied the Mexican As standard at flow rates of
environment of Al and As in EC flocs generated in Bajío ground- 0.91–2.73 cm s–1, corresponding to aluminum doses of 7–16 mg L–1
water, but this was beyond the scope of the present study. It and aluminum dose rates of 0.30–0.39 mg L–1 s–1. It should be
should be noted that CAs satisfies the WHO limit of ≤10 μg L–1 at noted that the cell potential decreased as a function of u at each
u ¼0.91 cm s–1 and the Mexican standard of ≤25 μg L–1 at u ¼0.91– current density, indicating that aluminum ions are transported
1.82 cm s–1. away from the surface to the bulk solution under such turbulent
At 5 mA cm–2, the behavior of CAs as a function of u differed for the flow conditions, decreasing Al2O3 precipitation on the anode. The
ranges 0.91–1.81, 1.81–2.73 and 2.73–4.55 cm s–1 (Fig. 3b). CAs is close best EC in terms of energy consumption was obtained at 4 mA cm–2
to zero at u¼0.91 cm s–1, 22 μg L–1 at u¼ 1.81 cm s–1 and 23 μg L–1 at and u¼1.82 cm s−1, for which energy consumption of 1.2 kWh m–3
u¼ 2.73 cm s–1. The latter slight variation in CAs can be attributed to reduced arsenic from 50 to 17 μg L–1. Data for carbonates, hardness,
the almost constant experimental aluminum dose of 6–7 mg L–1. CAs pH and conductivity are not presented, since these parameters
then increased linearly from 23 to 33 μg L–1 at 2.73–4.55 cm s–1 due to remained almost constant.
depletion of the experimental aluminum dose. Studies have shown that several dissolved species present in
At 6 mA cm–2, CAs as a function of u showed different behavior at water samples can interfere with EC arsenic removal. For example,
0.91–3.64 and 3.64–4.55 cm s–1 (Fig. 3c). The increase in CAs from 11 Wan et al. (2011) reported that phosphates in synthetic ground-
to 33 μg L−1 at 0.91–3.64 cm s–1 was significant, and CAs remained water interfere with EC arsenic removal using Fe as sacrificial
constant at 33 μg L–1 with a further increase to u¼4.55 cm s–1. anodes, because phosphate and As species compete with surface
In the presence of hypochlorite, the experimental dose of alumi- iron oxide sites. The authors also showed that silicates and sulfates
num was lower than the corresponding theoretical dose (Fig. 3a–c). did not affect As removal. However, reports regarding As removal
CAs after EC was lower in the presence of hypochlorite than by EC using Al electrodes are rather limited. Mohora et al. (2012)
without hypochlorite, indicating that arsenic removal is more reported that natural organic matter is simultaneously removed
efficient when arsenite is oxidized to arsenate. Arsenate removal with As from groundwater by EC using Al anodes. It should be
by EC might involve adsorption on aluminum hydroxides gener- noted that we did not measure concentrations of phosphates,
ated in the process. silicates, sulfates and natural organic matter, and hence their
Although the initial groundwater As concentration of 50 μg L–1 influence on As removal is not discussed. However, this analysis
complies with safety standards in many countries, the Mexican should serve as a useful starting point and these interferences may
authorities want to reduce the maximum acceptable level of be investigated in future research.
arsenic in drinking water from 25 to 10 μg L–1 because of chronic The experimental aluminum dose in the presence of hypochlorite
health problems in the population. Experiments were performed did significantly improve when the current density was increased
at 4 and 5 mA cm–2 and 0.81 cm s–1 (Table 3) with the aim of from 4 to 5 mA cm–2 and at 4 mA cm–2 it did not significantly differ in
obtaining residual arsenic concentrations of o10 μg L–1. the absence and presence of hypochlorite. These random discrepan-
Table 3 summarizes EC results that satisfy the Mexican arsenic cies are typically observed in electrodissolution processes. The experi-
standard of ≤25 μg L–1, including the cell potential (Ecell) and mental aluminum dose and aluminum dose rate in the presence and
electrolytic energy consumption, evaluated as absence of hypochlorite at 6 mA cm–2 were lower than those obtained
at 4 and 5 mA cm–2 due to massive generation of electrolytic gases
Econs ¼
Ecell I
ð10Þ and anode passivation. EC at 46 mA cm–2 did not lead to further
3:6 B S u removal of As (data not shown).
The random discrepancies for the experimental dose and dose
where I is the current intensity during electrolysis (C s–1), B is the
rate of aluminum at each flow rate did not systematically improve
channel height (cm), S is the channel width (cm) and 3.6 is a
with increasing current density (Table 3); these discrepancies
conversion factor used to obtain Econs in units of kWh m–3.
indicate a lack of correlation between As removal and the current
Table 3 reveals that EC at 4 mA cm–2 satisfied the Mexican
density and flow rate.
standard for arsenic at flow rates between 0.91 and 1.82 cm s–1,
Table 3
Residual arsenic concentrations after hypochlorite addition satisfying the Mexican 5. Conclusions
standard (CAs≤25 μg L–1), as well as the aluminum dose (CAl(III)) and dose rate
(QAl(III) ¼CAl(III)u/LT), cell potential and electrolytic energy consumption. We systematically investigated arsenic removal from Bajío
Current u CAs CAl(III) QAl(III) Ecell Econs
groundwater by EC using aluminum as a sacrificial anode in a
Density (cm s–1) (μg L–1) (mg L–1) (mg L–1 s–1) (V) (kWh m–3) pre-pilot-scale continuous filter press cell. The influence of current
density, mean linear flow rate and hypochlorite addition on the As
4 mA cm−2 0.91 3 17 0.32 8.4 2.5 removal efficiency was analyzed.
1.82 17 9 0.34 7.9 1.2
Poor removal of total As by EC in the absence of hypochlorite at
2.73 – – – – –
5 mA cm−2 0.91 0 31 0.58 10.6 3.9 current densities of 4, 5 and 6 mA cm–2 and mean linear flow rates
1.82 22 7 0.26 8.9 1.6 of 0.91–4.55 cm s–1 was due to a mixture of arsenite and arsenate.
2.73 23 6 0.34 8.9 1.2 Arsenic removal is more efficient when arsenite is oxidized to
6 mA cm−2 0.91 11 16 0.30 11.6 5.3 arsenate by addition of hypochlorite at a concentration typically
1.82 22 10 0.37 11.2 2.5
2.73 25 7 0.39 10.8 1.6
used for disinfection. Arsenate removal by EC might involve
adsorption on aluminum hydroxides generated in the process.
6 O.J. Flores et al. / Chemical Engineering Science 97 (2013) 1–6
The resulting sample meets the Mexican arsenic standard of Ghurye, G., Clifford, D., 2001. Laboratory Study on the Oxidation of Arsenic III to
≤ 25 μg L–1. Arsenic V. US EPA, Cincinnati.
Hansen, H.K., Henrik, K., Nunez, P., Jil, C., 2008. Removal of arsenic from waste-
EC investigations revealed that mean linear flow rates between waters by airlift electrocoagulation Part 2: Continuous reactor experiments.
0.91 and 2.73 cm s–1 at current densities of 4–6 mA cm–2 yielded Sep. Sci. Technol. 43, 3663–3675.
samples that met the Mexican standard for arsenic in water. Under Hansen, H.K., Nuñez, P., Raboy, D., Schippacasse, I., Grandon, R., 2007. Electro-
these conditions, aluminum doses and dose rates of 6–31 mg L–1 coagulation in wastewater containing arsenic: comparing different process
designs. Electrochim. Acta 52, 3464–3470.
and 0.26–0.58 mg L–1 s–1, respectively, were suitable. Hernández, J.R., Nava, J.L., Carreño, G., Martínez, F., 2010. Removal of arsenic (V) by
Complete arsenic removal by EC was achieved at 5 mA cm–2 electro-coagulation process, in: Birkle, P., Torres-Alvarado, I.S. (Eds.), Proceed-
and 0.91 cm s–1, with electrolytic energy consumption of ings of the 13th International Symposium on Water–Rock Interaction (WRI-13),
CRC Press/Taylor and Francis, London, 2010, pp. 583–585.
3.9 kWh m–3. The best EC in terms of energy consumption was Kobya, M., Gebeloglu, U., Ulu, F., Oncel, S., Demirbas, E., 2011. Removal of arsenic
obtained at 4 mA cm–2 and 1.82 cm s–1, with energy consumption from drinking water by the electrocoagulation using Fe and Al electrodes.
of 1.2 kWh m–3 to decrease arsenic from 50 to 17 μg L–3. Electrochim. Acta 56, 5060–5070.
An increase in current density to 46 mA cm–2 did not improve Martínez-Villfañe, J.F., Montero-Ocampo, C., García-Lara, A.M., 2009. Energy and
electrode consumption analysis of electrocoagulation for the removal of arsenic
the EC process any further. This is attributed to massive generation from groundwater. J. Hazard. Mater. 172, 1617–1622.
of electrolytic gases and anode passivation. Mohora, E., Roncevic, S., Dalmacija, B., Agbaba, J., Watson, M., Karlovic, E., Dalmacija,
M., 2012. Removal of natural organic matter and arsenic from underwater
electrocoagulation/flotation continuous flow reactor. J. Hazard. Mater. 235–236,
Acknowledgments 257–264.
Parga, J.R., Cocke, D.L., Valenzuela, J.L., Gomes, J.A., Kesmez, M., Irwin, G., Moreno,
H., Michael, W., 2005. Arsenic removal via electrocoagulation from heavy metal
We are grateful to CONACYT and CONCYTEG for financial support contaminated groundwater in La Comarca, Lagunera, Mexico. J. Hazard. Mater.
under the FOMIX GTO-2011-C03-162757 project. We thank Cynthia 124, 247–254.
Pourbaix, M., 1974. Atlas of Electrochemical Equilibria in Aqueous Solutions.
Montaudon for her help in revising the manuscript. We would also NACEHouston.
like to thank Universidad de Guanajuato for financial support. Ramos, Y., Ramírez, F., Martínez, J., Muñoz, D., Rodríguez, I., Carreño, G., 2011.
Affectations of the drainage of mines abandoned to the supply of drinking
water in Guanajuato, Mexico. Macla 15, 175–176.
References Rios, G.B., Almeraya, F., Herrera, M.T.A., 2005. Electrode passivation in the electro-
coagulation process. Port. Electrochim. Acta 23, 17–34.
American Public Health Association (APHA), 1995. Standard Methods for the Shen, F., Chen, X., Gao, P., Chen, G., 2003. Electrochemical removal of fluoride ions
Examination of Water and Wastewater, 19th ed. American Public Health from industrial wastewater. Chem. Eng. Sci. 58, 987–993.
Association/American Water Works Association/Water Pollution Control Federation, Smedley, P.L, Kinniburgh, D.G., 2002. A review of the source, behaviour and
New York. distribution of arsenic in natural waters. Appl. Geochem. 17, 517–568.
Amirtharajah, A., Clark, M.M, Trussell, R.R., 1991. Mixing in Coagulation and Smith, A.H., Marshall, G., Yuan, Y., Ferreccio, C., Liaw, J., von Ehrenstein, O.,
Flocculation. , American Water Works Association Research FoundationDenver. Steinmaus, C., Bates, M.N., Selvin, S., 2006. Increased mortality from lung
Balasubramanian, N., Kojima, T., Ahmed Basha, C., Srinivasakannan, C., 2009. cancer and bronchiectasis in young adults after exposure to arsenic in utero and
Removal of arsenic from aqueous solution using electrocoagulation. J. Hazard. in early childhood. Environ. Health Perspect. 114, 1293–1296.
Mater. 167, 966–969. van Genuchten, C.M., Addy, S.E.A., Peña, J., Gadjil, A.J., 2011. Removing arsenic from
Chen, X., Chen, G., Yue, P.L., 2002. Investigation on the electrolysis voltage of synthetic groundwater with iron electrocoagulation: an Fe and As K-edge
electrocoagulation. Chem. Eng. Sci. 57, 2449–2455. EXAFS study. Environ. Sci. Technol. 46, 986–994.
García-Lara, A.M., Montero-Ocampo, C., 2010. Improvement of arsenic electro- Wan, W., Pepping, T.J., Banerji, T., Chaudhari, S., Giammar, D.E., 2011. Effects of
removal from underground water by lowering the interference of other ions. water chemistry on arsenic removal from drinking water by electrocoagulation.
Water Air Soil Pollut. 205, 237–244. Water Res. 45, 384–392.